Arylphosphate compounds



United States Patent 2,982,685 ARYLPHOSPHATE COMPOUNDS Richard R. Whetstone and Alan R. Stiles, Modesto, Califl, assignors to Shell Oil Company,--New York, N.Y., a corporation of Delaware No-Drawing. Filed Dec. 23, 1957, Ser. No. 704,341

14 Claims. (Cl. 167-30) This invention relates to novel complex halogenated aryl compounds which contain phosphorus and to the employment of these compounds as insecticides. Certain organic phosphorus-containing compounds have become important in recent years because of their potency as insecticides. For example, Stiles, US; 2,685,552 (Shell Development Company), describes dimethyl-l-carbornethoxy-l-propen-Z-yl phosphate as an insecticide of outstanding toxicity. In spite of their impressive initial toxicity, many of these phosphorus compounds are effective for only a short time and are consequently rendered less valuable or altogether useless in those situations calling for extended residual toxicity. The need for potent phosphor-us-containing insecticides manifesting extended residual toxicity has thus become increasingly manifest. The novel insecticides of the present invention satisfy this urgent need without sacrificing the characteristic potency and other advantages of these known organicphosphorus insecticides. The principal object .of the present invention is then to provide organic phosphoruscontaining insecticidal compounds evidencing high initial potency, extended residual toxicity, yet which are relatively inexpensive to synthesize andformulate.

Another object of the present invention is to provide insecticidal compositions containing these compounds.

Yet another object of the present invention is to provide a method of combating insects comprising essentially contacting insects with these novel compounds.

Other objects, features and advantages of the present invention will be apparent from the following description read in conjunction with the appended claims.

The new and novel compounds encompassed by the present invention may be represented by the following structural formula:

wherein R is a halogenated (preferably chlorinated) aralkyl or aryl group. When R is an aralkyl group the alkyl portion may contain 1-5 carbon atoms and is a branched or straight chain. The alkyl portion ofthe aralkyl group is preferably methyl. The aryl portion of the molecule may be a phenyl or tolyl group. p A benzyl group is preferred. The aryl group is partially or completely halogenated, preferably with chlorine; R is a lower alkyl radical which may contain 1-5 carbon atoms. Methyl is preferred. Specific examples of compounds encompassed by the present invention are:

2 (p chlorophenoxycarbonyl)-1-methylvinyl-dimethy1 phosphate,

2-(p-chlorobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate,

2 (o-chlorobenzyloxycarbonyl)-1-methy1vinyl dimethyl phosphate,

2-(2,3-dichlorobenzyloxycarbonyl-1-methylvinyl dimethyl phosphate,

o-(3,4-dichlorobenzyloxycarbonyl)-1-methylvinyl dimethyl phosphate,

"ice

2 (p chloro-alpha-methylbenzyloxycarbonyl)-ll-methyl- VlIlYl dimethyl phosphate,

2-(5-(p-fluorophenyl)pentyloxycarbonyl)-1 methylvinyl dimethyl phosphate,

2-(p iodobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate,

2-(o-bromobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate,

Drmethyl-l-methyl-Z -'(2,3,4,5,6-pentachlorobenzyloxycar- 'bonyl)vinyl phosphate,

2-(p chlorotolyloxycarbonyl) 1 methylvinyl dimethyl phosphate, Y

2 (p chlorophenoxycarbonyl) 1 methylvinyl dipentyl phosphate,

2- (pgchlorobenzyloxycarbonyl-l-methylvinyl diethyl phosp ate.

The novel compounds of the present invention can be prepared by any of the methods known in the art for synthesizing compounds of this general character. If desired, compounds of the present invention may be prepared by reacting trialkyl phosphite with the appropriate halrlaarylhaloacetoacetate as shown in the following forum 21:

In this equation R is a halogenated aralkyl or aryl radical as defined above and R is a lower alkyl radical as defined above.

The preparations of the compounds of the present invention are illustrated by the followingexamples:

I. 2- (p-CHLOROPHENOXYCARBONYL) -1METHYL- VINYL DIMETHYL PHOSPHATE CH (I? p-Chlorophenyl 2-chloroacetoacetate (135 g., 0.545 mole) was placed in a 3-neck round bottom 300 cc. flask fitted with stirrer, dropping funnel and a- 4-tube carrying a thermometer and a reflux condenser attached to a Dry Ice acetone trap. The stirred material was heated to 80 C. and trimethyl phosphite (70 cc., 70.5 g., 0.593 mole) added slowly with stirring during a period of mmutes. The temperature was controlled between C. and C. 'After addition, the reaction mixture was heated to C. for one hour. Cold trap contents, 23 g., B.P. 24 C. (CH Cl). The bottoms were stripped to 60/ .05 mm. The stripped product was then stripped on the molecular still at 35/.005 mm., then at 100/0.0005 mm. The distillation was carried out at l35/.005 mm. Calc. 11.5%. C1 found 12.0. Calc. 10.02% P, found 9.3% P. The product was then stripped at 112-115/'0.000 1 mm. and distilled at 125- 130/0.0001 mm. Yield 55%. Analysis C H PO CI.

It will be understood that the corresponding diethyl-, dipropyl-, dibutyl-, and dipentyl phosphates may be prepared by employing triethyl-, tripropyl-, tributyl-, and tripentyl'phosphite separately.

II. 2-p-CHLOROBENZYLOXYCARBONYL-l-METH- YLVINYL DIMETI-IYL PHOSPHATE p-Chlorobenzyl 2-chloroacetoacetate (130 g., 0.497 mole( was placed in a 300 cc. round bottom three-necked flask fitted with dropping funnel, mechanical stirrer and 4-tube carrying a thermometer and a reflux condenser attached to a Dry Ice-acetone cold trap for collecting Ch Cl. The stirred material was heated to 80 and trimethyl phosphite added dropwise (71 cc., 92% pure), the temperature of the reaction being controlled between 80 and 100 during the addition (1 hour). The reaction mixture was heated to 120-130 and stirred for an additional hour. The product was stripped to 100 by house vacuum and then to 100/.05 mm. but no distillate collected. The cold trap contents before stripping weighed 23 g. The reaction mixture was then stripped on the molecular still, 171 g. crude giving 167 g. residue after stripping at 5860/ .0005 mm. This residue was distilled on the molecular still at 138-140/ .0005 mm. The distillate obtained weighed 152 g. The residue, weighing 11 g. was discarded. Yield 91.5%. Analysis C H PO 'CI;

It will be understood that the corresponding diethyl-, dipropyl-, dibutyl-, and dipentyl phosphates may be prepared by employing triethyl-, tripropyl-, tributyl-, and tripentyl phosphite respectively.

o-CHLOROBENZYL 3-(DIMETHOXYPHOS- PHINYLOXY) CROTONATE CHaCO CHzCOO CHzQ-l-SOaClz- (CHaCO CHCICIIO O CHz +sOz+HCl 4 ture (25) in the course of /2 hour. The product was degassed up to a temperature of 50 using house vacuum for /2 hour, then maintained at 50 for another /2 hour at 72 mm. The slightly yellow solution was now heated to 60 and 66.0 g. (0.56 mole) of (CH O) P was added during the course of one hour controlling the temperature between 60-65 with stirring. The escaping CH Cl was collected in a Dry Ice-acetone trap. After the final addition, the temperature was raised to 70-75 for /2 hour and then vacuum applied (to remove as much as possible of the CH Cl) for /2 hour. 24.0 g. of CH Cl (90.5% of theory) was obtained. The slightly colored solution was stripped at'100-125/10- mm. The prodnot was distilled at 150;"/10- rmn. There were obtained 49 g. (43.0 cc.) of residue (light yellow in color) and 87.0 g. (75 cc., d=1.2) of almost colorless distillate. More distillate is obtained it slower distillation is employed. Yield=52%. C H ClO -P calc.: C, 46.7, H, 4.6; Cl, 10.6; P, 9.3. Found: C, 46.9; H, 4.9; Cl, 10.6; P, 8.5.

It will be understood that the corresponding homologs may be made by employing triethyl-, tripropyl-, tributyl-, and tripentyl phosphite, respectively.

IV. 2,4-DICHLOROBENZYL 3-(DIMETHOXYPHOS- PHINYLOXY) CROTONATE OHaE=CHCOOOH+GHaCl liquid was cooled to 10 and 43.0 cc. of SO Cl (0.53

mole; 71.5 g.) was added dropwise during the course of 1 hour. The temperature was maintained at 10-15 using ice-cooling when necessary. After the final addition, the temperature was allowed to rise to ambient tempera- 2,4-dichlorobenzyl acetoacetate (94 g.; 0.36 mol) was cooled to 10 andwhile stin'ng 45.5 g. (27.0 cc.; 0.337 mol) of SO CI were added dropwise during the course of 30-40 minutes. The temperature was maintained at 1015 C. After the final addition the temperature was allowed to come to ambient temperature /2 hour) and the S0 and HCl removed by applying house vacuum for /2 hour at 50 and Hy-Vac (5 mm.) at 50 for another /2 hour. The resulting yellow oil was stirred and heated to 70 and (CH O) P (45.0 g.; 0.36 mol) was added dropwise during A2 hour While maintaining the temperature between 75-80. After the final addition the reaction mixture was maintained at 7580 for /2 hour and allowed to stand overnight.

The reaction mixture was stirred and heated to 75 and house vacuum applied for /2 hour. 16.0 g. of CH Cl was obtained in the trap (95% theory). The oil was then stripped at /10- mm. The stripped material dis tilled at 170180/10- mm. to yield 95.0 g. of yellow oil. Volume=70 cc., d=1.3, n =1.5273. Yield: 76.7%. 10 cc of residue and 5 cc. of colorless liquid in the trap were also obtained. Calc.: for C H Cl O P: C, 42.3; H, 4.1; Cl, 19.3; P, 8.4. Found: C, 42.4; H, 4.6; Cl, 20.1; P, 8.0. The sample was redistilled at -5 /10- mm. These was obtained 58.0 ml. of yellow oil having a weight of 80.0 g. (yield=65%; d=1.3), n 1.5272.

It will be understood that the corresponding homologs and tripentyl phosphite, respectively.

A CHgO COCHCICO CHa+(CHaO)sP- v Y Cl CHaC1+ 3,4-dichlorobenzyl 2-chloroacetoacetate (78 g., 0.264 mole) was treated withtrimethyl phosphite (36 g., 34 cc., representing a 10% excess) at 80. The reaction was exothermic. and external cooling was required to keep the temperature of the mixture at or below 100 during the addition, which required 18 minutes. After addition was complete the temperature was raised to 125 for one hour. 11 g. of material, boiling below room temperature were collected in the cold trap. (Calc. for CH Cl, 13.3 g.) The reaction mixture was then stripped for 30 minutes at 125 and house vacuum employed. An additional 1 g. of material was collected in the cold trap. The reaction mixture was then stripped on the molecular still at 117120/.0005 mm. yielding a distillate of 8 g., n 1.5265, d 1.45 and a residue of 84 g. Crude yield 86.2%. The residue was distilled on the molecular still at 160/ .0005 mm. to give a distillate, 77 g., 11, 1.5278, d 1.32 and a residue 4 g., n 1.5431, d 1.33, which was discarded. Yield 79%. The distillate analyzed as follows: C H PO Cl (369.15).

Percent Percent Percent Percent I 11,,

C H 01 P 42. 29 4. 10 19. 21 8. 39 Found 42. 7 4. 2

Itwill be understood that the corresponding homologs may be made by employing triethyl-, tripropyl-, tributyl-, and tripentyl phosphite, respectively.

VI. p-CHLORO-ALPHA-METHYLBENZYL-3-(DI- METHOXYPHOSPHINYLOXY) CROTONATE H on, 0 01 CIQiI 01" 0 CH3):

to 50-55 for 15 minutes during which time S05 and a 6 trap; This was followed" by the removal of residual S0 +HCl using Hyvac 2 mm.) at 50 for 15 minutes. The slightly coloredsolution was heated and stirred at 65-70 while,(CH O) P (49.5 g.; 0.40 mol) was added during the course of 1% hours. The reaction mixture was then stirred and heated at 70-75 for V2 hour, cooled and allowed to stand overnight. I

The yellow reaction mixture was heated to 7580 with stirring and house vacuum applied for /2 hour. The total weight of- CH CI obtained in the Dry Ice trap was 19.0 g. (Theory required 18.5 g.) The yellow solution was stripped at 13,0/10-' mm. cc. g.) of a yellow (stripped) viscous liquid and 20 cc. (20.0 g.) of distillate (yellow in color) was obtained.

This residue was distilled at 150/10- mm. yielding 69 cc. (86.0 g.) of yellow distillate and 10.0 cc. of brown residue plus 11.0 cc. of colorless liquid in trap with odor of (CH3O) P. The distillate was redistilled and stripped at 140/10" mm. Overall yield 31%. Analysis: C H ClO P.

C H 01 P Cale 48.3 5.2 10.0 8.9 Found 47.9 4.4 10.2 8.5

It will be understood that the corresponding homologs may be made by employing triethyl-, tripropyl-, tributyl-, and tripentyl phosphite, respectively.

VII. 2,3,4,5,6 PENTACHLOROBENZYL 3 (DIMETH- OXYPHOSPHINYLOXY) CROTONATE 69 g. of pentachlorobenzyl 2-chloroacetoacetate and 500 cc. xylene was placed in a 1 liter three necked round bottom flask fitted with dropping funnel, mechanical stirrer and four tube bearing a thermometer and reflux condenser attached to a Dry Ice acetone cold trap. The mixture was stirred and heated to 80 C. 26.5 g. of trimethyl phosphite was added dropwise with continued heating. After twenty minutes the temperature of the reaction was raised to -135 and maintained at this temperature for four hours. After cooling the contents of the flask was transferred to a distillation kettle and the reaction flask rinsed out with xylene. The washings were added to the reaction mixture. The viscous oily residue solidified on standing and was subsequently washed with ether leaving a white: solid, melting point 118-121". Cooling of the ether washings gave a white precipitate which was removed by suction filtration. The solid was dissolved in acetone and crystallized on standing. The white solid was filtered and dissolved in acetone and left to crystallize. The white solid was collected and the filtrate was combined with previous filtrates and evaporated. Ether was added to the oily residue to produce crystallization. After completion of filtration the remaining solid was washed with ether and the fil'trated' wash was combined and stripped; The non solid residue was distilled on a molecular still.

Yielded 8 g. of distillate, 42 g. of brownish liquid wash. Analysis is as follows: I

Percent Percent Percent Percent C H 01 P Relative toxicity (toxicity index) LD of the standard LD of a test sample In these tests dieldrin was used as a standard for tests against houseflies and southern army worms. Parathion was employed as a standard with pea aphids, Mexican bean beetle larvae and two-spotted spider mites. The quantity of standard employed to give 50% mortality of the insects in each test was arbitrarily given a numerical value of 100. The toxicity of a representative product of the invention against the common housefly (Musca domestica) was determined generally following the method described by Y. P. Sun, Journal of Economic Entomology, volume 43, page 45 et seq. (1950). Solutions or emulsions of representative compounds were made up by employing acetone, a neutral petroleum distillate lying within the kerosene range as a solvent. These solutions were tested for toxicity against insects listed in the table by spraying groups of plants infested with the insects under controlled conditions which varied from test to test only in the concentration of toxicant.

In the case of two-spotted spider'mites rotating preinfested bean plants were sprayed at low volume through a horizontal tunnel with water solutions or suspensions of the toxicants by the method described by Dorman and Hall- (Journal Economic Entomology 46; 151, 1953). Mammalian toxicity tests were also conducted on male mice.

As this table clearly shows outstanding insecticidal activity, particularly against mites :was evidenced by:

2-'(p-chlorophenoxycarbonyl) 1- methylvinyl dimethyl phosphate 2-(o-chlorobenzyloxycarbonyl) l methylvinyl dimethyl phosphate 1 2 (2,4 dichlorobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate 2 (3,4 dichlorobenzyloxycarbonyl) 1 methylvinyl dimethyl phosphate That the compounds of the present invention exhibit a surprising residual toxicity when compared with 2- (methoxycarbonyl)-1-methylvinyl dimethyl phosphate, is illustrated by tests. conducted against the boll weevil, two-spotted mite, and Mexican bean beetle.

The initial and residual toxicity of each of the compounds vof the present invention to boll weevils when sprayed at the rate of 0.5 lb./acre on boll weevils caged on field treated cotton plants was ascertained. 2-(methoxycarbonyl)-1-methylvinyl dimethyl phosphate was found to be ineffective two days after spraying whereas the compounds of the present invention exhibited significant toxicity after three days.

Against the two-spotted mite, pre-infested bean plants were treated with low volume sprays of the testchemical at concentrations of 20 and 40 times its LD value, i.e.

the amount by weight of test chemical effecting a 50% initial insect kill. Seven days after spray, total living mites were counted and expressed as percent reduction from the check. The compounds of the present invention were superior to 2-(methoxycarbonyl)-l-methylvinyl dimethyl phosphate in all recorded tests.

compounds of the present invention evidenced insecticidal activity seven days after spraying whereas Z-(methoxycarbonyl) l-methylvinyl dimethyl phosphate evidenced no activity at this time. The following table summarized the experiments illustrating the residual toxicity of the compounds of the present invention when-compared to 2-(methoxycarbonyl)-1-methylvinyl dimethyl phosphate.

Insecticidal toxicity of complex halogenated aryl compounds [Toxicity index (standard=100)] Mexican Southern Two- Toxicity House Fly Pea Aphid Bean Army- Spotted Male Compound Name Dieldrin I Parathion Beetle worm Spider Mice,

Larva Dieldrin 1 Mite Mg./Kg. Parathion 1 Parathion 1 2- (o- Chlorophenoxycarbonyl) -1- methylvinyl dimethyl phosphate 10 5 15 48 7 33 250-500 2- (p- Chlorobenzyloxy-carbonyl) l-methylvinyl dimethyl phosphate 22 56 53 14 254 212 2- (o Ohlorobenzyloxycarbonyl) l-methylvinyl dimethyl phosphate a. 11 6O 19 113 77 2 (2,4 Diehlorobenzyloxy car bonyD-l-methylvinyl dimethyl phosphate 9. 6 20 65 14 117 2 (3,4 Dichlorohenzyloxy -car bonyD-l-methylvinyl dimethyl phosphate 9. 6 12 52 22 111 117 2- (p-Chloro-alpha-methylbenzyloxycarbonyl) 1 methyl vinyl dimethyl phosphate 24 56 107 74 74 154 Standard.

tobeprotected by'Un'ited States Letters Patent is;

Boll Weevil at 0.5 2-Spotted Mexican Bean lb./a.ere-Days after mite 7 days Beetle at 10 spray at factor XLDso at days Compound Name XLD after spray 2 Methoxycarbonyl) 1 methyl vinyl dimethyl phosphate 96 36 0 59 78 0 2 (p Chlorobenzyloxycarbonyl) methyl vinyl dimethyl phosphate 85 90 35 55 97 100 93 90 23 2- o Chlorob euzyloxycarbonyll- 1 methyl vinyl dimethyl phosphate so 50 90 30 93 99 100 67 2- (2,4-Dichlorobenzyloxycarbonyl) -1 -methylvinyl dimethyl phosphate 30 65 31 45 100 100 100 97 2 (3,4 Dichlorobenzyloxycarbonyl) l methyl vinyl dimethyl phosphate 10 85 35 65 100 100 100 97 Dimethyl l-methyl-2-(2,3,4,5,6-pentachlorobenzyloxycarbonyDvinyl phosphate 30 30 99 99 100 87 2- (p- Ohloro-alphamethylbenzyloxycarbonyl) -1- methylvinyl dimethyl phosphate..- 91 100 100 57 The compounds of this'invention can be employed for 1. A compound of the general formula insecticidal purposes by the use of any of the methods CH3 0 which are conventionally employed in the art.- For ex- (RIO) O O R ample, the compounds cancither be sprayed or otherwise applied in the form of a solution or dispersion, or 25 wherein R is Sekcted from the p Consisting of lotbey can be absorbed on an inert, fi l divided 5d genated mononuclear aryl and halogenated mononuclear and applied as a dust.. Useful solutions for application aralkyl Iadlcals Where111the a1ky1m0i6ty Contains from 1 by spraying, brushing, dipping, and the like, can be to 5 carbon atoms, and R is an alkyl radical of from 1 pared by using as the solvent any of the Well-known inert to 5 caljbon alOmS- I horticultural carriers, including neutral hydrocarbons -(P P Y Y YD y y such as kerosene and other light mineral oil distillates Phosphate Whefem each of the Y groups Contains of intermediate viscosity and volatility. Adjuvants, such from 5 C r n atoms. as spreading or wetting agents, can also be included in Dlalky'l p ay y y r nyl) 1 meththe solutions, representativematerials of this character Y Y P P1 wherein each of the alkyl E P and vbemg fatty acid soaps, rosin salts, sapomns, gelatine, alkyl molety of the halopheflylalkyloxy g p casein, long-chain fatty alcohols, alkyl aryl sulfonates, tfllns from 1 t0 5 Carbon atoms. 1 long-chain alkyl sulfonates, phenolethylene oxide con- 2 (P chlorophenoxycal'bonyl) 1 methylvillyl densates, C to C amines and ammonium salts, and the dlmethyl P p like. These solutions can be employed as such, or more 2 chlol'obenzyloxycarbonyl) 1 t y vinyl preferably, they can be dispersed or emulsified in water dlmethyl P P Q and the resulting aqueous dispersion or emulsion applied dlc1l1ol'obenzyloxycal'bonyl) 1 ylas a spray. Solid carrier materials which can be em- V1I1Y1 dlmelhyl Ph p ployed include, talc, bentomte, lime, gypsum, pyrophyldlchlorobenzyloxylcafbonyl) 1 m hyllite and similar inert solid diluents. If desired, the com- Vmyl dlmethyl P p I pounds of the present invention can be employed as 2 (P 1 alpha methylbenzyloXycarbonyD- ierosols, asfby dispersingdthe same into the atmosphere -g %g fli g i y P 8 5 t hi h y means 0 acompresse gas. I e me o 0 com ainginsecs w c comprises The concentration of the compounds to be usedwith a p to insect habitats P of im the above carriers is dependent upon many factors, in- @ethod 1 W cflmprises. cluding the particular compound utilized, the carrier ernapplymg lnsectlhabltats a CfJmPOUIId of Claim 2-' ployed, the method and conditions of application, and method of c'ombatmg insects which f o p the insecticide species to be controlled, at proper 0011- PP Y Insect 11211311315 a nd of clalm sideration and resolution of these factors beingwithin Dlauiyl 2 (halobelllyloxycal'bonyl) 1 y the skill of those versed in the insecticide art, -I n gen- 5 Y1P P P- f b r eral, however, the compounds of this invention are effec -d 1 3 ailunseicticidal colmp l w of matter a tive in concentrations of from about 0.01-to 0.5% based 11 0 6 31m pp 111 a 3 i d inert upon th t l i h f th p iti th h d carrier material, the concentration of said compound besome circumstances as little as about 0.0000l% or as from about 0130001 110 21190111 2 Percent of I as or e venlmore of the compound can be em. bined said carrier material. plovyeiad with glooddresults from andinsecticidal stzgidpoiligt. -d' f ik f gf P l:1 9f i i 1 en emp eye as an insectici e a compoun o t is P01111 0 31111 lssemma e 1 an 1116f 0111611 mla invention can be employed either as the sole toxic in- Carrier-liquid, the concentration o Saidcompoundrbeiflg gredient or the insecticidal'composition or'it can be'emm about Q- QQ 10 about 2 percentof h fm h ed ployed 1n COIljlJIlClLlOB with the other insecticidally-active Welghts of $2116 po andsfl-ld m r materlal. 7 materials. Representative insecticides of this latter class y include the naturally-occurring insecticides such as 'ee C the file 0f P te pyretrum, rotenone, sabadilla', and the like, as well as the i UNITED STATES PATENTS various syntheti 'insecticides; including DDT, benzene, 2 532,204 Kosolapofi Ja11.',8, 19 52 hexachlonde, thlodlphenylamme, cy d t vl 2,802,855 Whetstone Aug. 13,1957 Py p p diethyl-p-nitropheriyl thiophosphate, 2 ,816,128" Aliens. e Dec. 10,1957 f benzene, and the various, compounds of arseniclead, .1; 2,826,529 Shapiro 1 "Ma r. 11, 1958 and/orfluorine. p r 2,830,069 Smith 7 ,Apr.- 8-, 1 958 Having thus, described this invention what is desired 2,838,478 Hillyer-Q; June 10, 1958 

1. A COMPOUND OF THE GENERAL FORMULA
 9. THE METHOD OF COMBATING INSECTS WHICH COMPRISES APPLYING TO INSECT HABITATS A COMPOUND OF CLAIM
 1. 13. AS AN INSECTICIDAL COMPOSITION OF MATTER A COMPOUND OF CLAIM 1 SUPPORTED UPON A FINELY DIVIDED INERT CARRIER MATERIAL, THE CONCENTRATION OF SAID COMPOUND BEING FROM ABOUT 0.00001 TO ABOUT 2 PERCENT OF THE COMBINED WEIGHTS OF SAID COMPOUND AND SAID CARRIER MATERIAL. 